Keratin dyeing compounds, keratin dyeing compositions containing them, and use thereof

ABSTRACT

Compositions for the oxidative dyeing of keratin fibers, comprising a medium suitable for dyeing and one or more bicyclic 5-6 heteroaromatic keratin dyeing compounds with one ring junction nitrogen one or two extra heteroatoms. A method for oxidative dyeing of keratin fibers, comprising applying such compositions in the presence of an oxidizing agent, for a period sufficient to develop the desired coloration.

CROSS REFERENCE TO RELATE APPLICATION

This application claims the benefit of provisional application Ser. No.60/557,787 filed Mar. 30, 2004.

FIELD OF INVENTION

This invention relates to bicyclic 5-6 heteroaromatic keratin dyeingcompounds with one ring junction nitrogen and one or two extraheteroatoms, compositions for the oxidative dyeing of keratin fibers(preferably hair) comprising such compounds, and use thereof.

BACKGROUND OF THE INVENTION

The most extensively used method currently employed to color hair is byan oxidative process that utilizes one or more oxidative hair coloringagents in combination with one or more oxidizing agents.

Commonly, a peroxy oxidizing agent is used in combination with one ormore developers or couplers, generally small molecules capable ofdiffusing into hair. In this procedure, a peroxide material, such ashydrogen peroxide, activates the developers so that they react with thecouplers to form larger sized compounds in the hair shaft to give avariety of shades and colors.

A wide variety of developers and couplers have been employed in suchoxidative hair coloring systems and compositions. However, there stillexists a need for additional keratin dyeing compounds that can act asboth developers and couplers that safely provide color benefits.

SUMMARY OF THE INVENTION

This invention relates to bicyclic 5-6 heteroaromatic keratin dyeingcompounds with one ring junction nitrogen and one or two extraheteroatoms according to the formulas defined herein. This inventionalso relates to a composition for the oxidative dyeing of keratinfibers, comprising a medium suitable for dyeing and one or more bicyclic5-6 heteroaromatic keratin dyeing compounds with one ring junctionnitrogen and one or two extra heteroatoms. This invention furtherrelates to a method for oxidative dyeing of keratin fibers, comprisingapplying such compositions in the presence of an oxidizing agent, for aperiod sufficient to develop the desired coloration. The keratin dyeingcompounds of the present invention can act as a developer and/or acoupler.

It is to be understood that within the scope of this invention, numerouspotentially and actually tautomeric compounds are involved. Thus, forexample, 2-mercaptopyridine (I) exists under known conditions in thepyridine-2-thione tautomer form (II).

It is to be understood that when this development refers to a particularstructure, all of the reasonable additional tautomeric structures areincluded. In the art, tautomeric structures are frequently representedby one single structure and the present invention follows this generalpractice.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims that particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

The present invention relates to bicyclic 5-6 heteroaromatic keratindyeing compounds with one ring junction nitrogen and having one or twoextra heteroatoms. The compounds of the present invention can act asdevelopers and/or couplers that safely provide color benefits.

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. Thecompounds/compositions and methods/processes of the present inventioncan comprise, consist of, and consist essentially of the essentialelements and limitations of the invention described herein, as well asany of the additional or optional ingredients, components, steps, orlimitations described herein.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified. The term “weight percent” may be denoted as “wt. %” herein.

Except as otherwise noted, all amounts including part, percentages, andproportions are understood to be modified by the word “about”, andamounts are not intended to indicate significant digits. Except asotherwise noted, the articles “a”, “an”, and “the” mean “one or more”.

As used herein, the term “keratin” refers to a scleroprotein found inepidermal tissues and modified into hard structures such as horns, hair,and nails. Thus, “keratinous fibers” refers to those found in hair, skinand nails and various animal body parts such as horns, hooves andfeathers.

As used herein, the term “hair” refers to keratinous fibers on a living,e.g. a person, or non-living body, e.g. in a wig, hairpiece, or otheraggregation of non-living keratinous fibers. Mammalian, preferablyhuman, hair is a preferred. Notably, hair, wool, fur, and otherkeratinous fibers are suitable substrates for coloring by the compoundsand compositions described herein.

As used herein, the term “keratin dyeing compounds” refers to compoundsthat may be used in the composition to act as developers, couplers, orboth, in order to provide color to ketatinous fibers.

As used herein, the term “keratin dyeing composition” refers to thecomposition containing one or more keratin dyeing compounds, includingthe compounds described herein.

As used herein, “cosmetically acceptable” means that ingredients whichthe term describes are suitable for use in contact with the skin or hairof humans and lower animals without undue toxicity, incompatibility,instability, irritation, allergic response, and the like.

I. Keratin Dyeing Compounds

The inventive compounds are bicyclic 5-6 heteroaromatic keratin dyeingcompounds with one ring junction nitrogen and one or two extraheteroatoms according to the following formulas:

wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are the same or different and areselected from the group consisting of:

(a) C-linked monovalent substituents selected from the group consistingof:

-   -   (i) substituted or unsubstituted, straight or branched, alkyl,        mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems,    -   (ii) substituted or unsubstituted, mono- or poly-cyclic        aliphatic, aryl, or heterocyclic systems, and    -   (iii) substituted or unsubstituted, mono-, poly-, or per-fluoro        alkyl systems; wherein said systems of (i), (ii) and (iii)        comprise from about 1 to about 10 carbon atoms and from about 0        to about 5 heteroatoms selected from the group consisting of O,        S, N, P, and Si;    -   wherein substituents of the substituted systems of the C-linked        monovalent substituents are selected from the group consisting        of amino, hydroxyl, alkylamino (linear, branched, or cyclic        C1-C5), dialkylamino (linear, branched, or cyclic C1-C5),        hydroxyalkylamino (linear, branched, or cyclic C1-C5),        dihydroxyalkylamino (linear, branched, or cyclic C1-C5),        arylamino or substituted arylamino (substituents are halogen,        C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5        alkylamino), heteroarylamino or substituted heteroarylamino        (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,        trifluoromethyl, amino, C1-C5 alkylamino), arylmethylamino or        substituted arylmethylamino (substituents are halogen, C1-C5        alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),        and heteroarylmethylamino or substituted heteroarylmethylamino        (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,        trifluoromethyl, amino, C1-C5 alkylamino),

(b) S-linked monovalent substituents selected from the group consistingof SA¹, SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²;

(c) O-linked monovalent substituents selected from the group consistingof OA¹, and ONA¹A²;

(d) N-linked monovalent substituents selected from the group consistingof NA¹A², (NA¹A²A³)⁺, NA¹OA², NA¹SA², NO₂, N═NA¹, N═NOA¹, NA¹CN, andNA¹NA² A³;

(e) monovalent substituents selected from the group consisting of COOA¹,CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A², CN, and X;

(f) fluoroalkyl monovalent substituents selected from the groupconsisting of mono-, poly-, and per-fluoro alkyl systems comprising fromabout 1 to about 12 carbon atoms and from about 0 to about 4heteroatoms; and

(g) hydrogen;

wherein A¹, A², and A³ are monovalent and are independently selectedfrom the group consisting of: H; substituted or unsubstituted, straightor branched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,aliphatic, heteroaliphatic, or heteroolefinic systems; substituted orunsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclicsystems; and substituted or unsubstituted, mono-, poly-, per-fluoroalkyl systems or A¹ and A² together with nitrogen atom to which they arebound form a ring; wherein said systems comprise from about 1 to about10 carbon atoms and from about 0 to about 5 heteroatoms selected fromthe group consisting of O, S, N, P, and Si;

wherein X is a halogen selected from the group consisting of F, Cl, Br,and I.

In a preferred embodiment, R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are selectedfrom the group consisting of a hydrogen atom; a halogen atom such aschlorine, bromine or fluorine; an amino substituent, a hydroxylsubstituent; a cyano substituent; a C₁-C₄ alkyl substituent; atrifluoromethyl substituent, an alkylamino substituent (e.g.,N,N-dimethylamino, N,N-diethylamino, N-methylamino, or N-ethylamino); ahydroxyalkylamino substituent (e.g., N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino or N,N-bis(hydroxypropyl)amino); anacetylamido substituent; a carboxyl substituent or its estes; an alkoxysubstituent (e.g., methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, phenoxyethoxy,p-chlorobenzyloxy or methoxyethylcarbamoylmethoxy); an alkoxyalkylsubstituent (e.g., methoxymethyl, methoxyethyl, methoxypropyl,ethoxymethyl, ethoxyethyl or ethoxypropyl); a carbamoyl substituent; analkylcarbamoyl substituent (e.g., methylcarbamoyl, ethylcarbamoyl,dimethylcarbamoyl, or diethylcarbamoyl); a hydroxyalkylcarbamoylsubstituent (e.g., 2-hydroxyethylcarbamoyl,bis(2-hydroxyethyl)carbamoyl, hydroxymethylcarbamoyl,bis(hydroxymethyl)carbamoyl); an amido substituent; an alkylamidosubstituent (e.g., acetamido, propionamido, or butyramido); analkylcarbonyl substituent (e.g., acetyl, butyryl, or propionyl), analkoxycarbonyl substituent (e.g., methoxycarbonyl, ethoxycarbonyl, orpropoxycarbonyl); an aryloxy substituent (e.g., phenoxy,4-methoxyphenoxy, 4-nitrophenoxy, 4-cyanophenoxy,4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, 3-methylphenoxyor 1-naphthyloxy); an acyloxy substituent (e.g., acetoxy, propanoyloxy,benzolyloxy, 2,4-dichlorobenzolyloxy, ethoxyalkyloxy, pyruviloyloxy,cinnamoyloxy or myristoyloxy); an alkylthio substituent (e.g.,methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio,benzylthio, phenethylthio, 2-(diethylamino)ethylthio, ethoxyethylthio orphenoxyethylthio); an arylthio substituent (e.g., phenylthio,4-carboxyphenylthio, 2-ethoxy-5-tert-butylphenylthio,2-carboxyphenylthio or 4-methanesulfonylphenylthio); a heteroarylthiosubstituent (e.g., 5-phenyl-2,3,4,5-tetrazolyloxy or2-benzothiazolyloxy); a heteroaryloxy substituent (e.g.,5-phenyl-2,3,4,5-tetrazolyloxy or 2-benzothiazolyloxy); a 3-, 4-, 5-,6-, or 7-membered heterocycle having at least one nitrogen, oxygen orsulfur atom (e.g., pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, oxazolyl, imidazolyl, thiadiazolyl,pyrollidine, piperidine, morpholine, piperazine, indoline,hexahydroazepine, aziridine, and azetidine) and being optionallysubstituted; an aryl substituent (e.g., phenyl or naphthyl) which isoptionally substituted; a sulfonyl substituent; a sulfinyl substituent;a phosphonyl substituent; a sulfamoyl substituent; a siloxy substituent;an acyloxy substituent; a carbamoyloxy substituent; a sulphonamidesubstituent; an imide substituent; a ureido substituent; asulfamoylamino substituent; an alkoxycarbonylamino substituent; anaryloxycarbonylamino substituent; an aryloxycarbonyl substituent; and abenzenesulfonamido substituent.

If the compound of the present invention is utilized as a developer, atleast one of R¹ or R³ is an amino group, with at least one of theremaining R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ being selected from the groupconsisting of amino, hydroxyl, a 3-, 4-, 5-, 6-, or 7-memberedheterocycle having at least one nitrogen, oxygen or sulfur atom (e.g.,pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl,triazolyl, tetrazolyl, oxazolyl, imidazolyl, thiadiazolyl, pyrollidine,piperidine, morpholine, piperazine, indoline, hexahydroazepine,aziridine, and azetidine) and being optionally substituted, alkylamino(linear, branched, or cyclic C1-C5), dialkylamino (linear, branched, orcyclic C1-C5), hydroxyalkylamino (linear, branched, or cyclic C1-C5),dihydroxyalkylamino (linear, branched, or cyclic C1-C5), arylamino orsubstituted arylamino (substituents are halogen, C1-C5 alkyl, C1-C5alkoxy, trifluoromethyl, amino, C1-C5 alkylamino), heteroarylamino orsubstituted heteroarylamino (substituents are halogen, C1-C5 alkyl,C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino), arylmethylaminoor substituted arylmethylamino (substituents are halogen, C1-C5 alkyl,C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino), andheteroarylmethylamino or substituted heteroarylmethylamino (substituentsare halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5alkylamino).

If the compound of the present invention is utilized as a coupler, atleast one of R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ is selected from the groupconsisting of hydrogen, amino, hydroxyl, alkylamino (linear, branched,or cyclic C1-C5), hydroxyalkylamino (linear, branched, or cyclic C1-C5),arylamino or substituted arylamino (substituents are halogen, C1-C5alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),heteroarylamino or substituted heteroarylamino (substituents arehalogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5alkylamino), arylmethylamino or substituted arylmethylamino(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, C1-C5 alkylamino), and heteroarylmethylamino or substitutedheteroarylmethylamino (substituents are halogen, C1-C5 alkyl, C1-C5alkoxy, trifluoromethyl, amino, C1-C5 alkylamino).

The couplers of the present invention can also accommodate nucleofugicleaving groups selected from the group consisting of hydrogen, chlorine,cyano, alkoxy, phenoxy, methylsulfonyoxy, pyridone and pyridazone.

In a preferred embodiment, the couplers of the present invention areutilized in compositions together with suitable 5-membered ringdevelopers chosen from the following classes: thiophenes, pyrroles,furans, pyrazoles, imidazoles, thiazoles, oxazoles, isothiazoles, orisoxazoles. In a more preferred embodiment, the couplers of the presentinvention are utilized in compositions together with with developersthat are pyrazoles. In an even more preferred embodiment, the couplersof the present invention are utilized in compositions together with thefollowing pyrazole developers: 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine and1-hydroxyethyl-4,5-diaminopyrazole sulphate. Even more preferably, thecouplers of the present invention are utilized in compositions togetherwith 1-methyl-1H-pyrazole-4,5-diamine;1-hydroxyethyl-4,5-diaminopyrazole sulphate; and2-(4,5-diamino-1H-pyrazol-1-yl)ethanol. While not being bound to theory,such combinations enable the achievement of desired more hypsochromiccolors (e.g., yellow) relative to conventional combinations ofdevelopers and couplers.

Preferably, the inventive compounds may be an unsubstituted orsubstituted member selected from the group consisting ofH-pyrrolo[1,2-b]pyridazine, H-pyrrolo[1,2-f]pyrimidine,H-pyrrolo[1,2-a]pyrazine, H-pyrrolo[1,2-a]pyrimidine,H-imidazo[1,5-a]pyridine, pyrazolo[1,5-b]pyridazine,pyrazolo[1,5-f]pyrimidine, pyrazolo[1,5-a]pyrazine,imidazo[1,5-b]pyridazine, imidazo[1,5-f]pyrimidine,imidazo[1,5-a]pyrazine, imidazo[1,5-a]pyrimidine,imidazo[1,2-b]pyridazine, imidazo[1,2-f]pyrimidine,imidazo[1,2-a]pyrazine, and imidazo[1,2-a]pyrimidine. More preferably,inventive compounds are an unsubstituted or substituted member selectedfrom the group consisting of H-pyrrolo[1,2-a]pyrimidine,pyrazolo[1,5-f]pyrimidine, imidazo[1,5-f]pyrimidine,imidazo[1,2-b]pyridazine, imidazo[1,2-f]pyrimidine, andimidazo[1,2-a]pyrimidine. Even more preferably, inventive compounds anunsubstituted or substituted member selected from the group consistingof H-pyrrolo[1,2-a]pyrimidine, imidazo[1,5-f]pyrimidine,imidazo[1,2-f]pyrimidine, and imidazo[1,2-a]pyrimidine.

Preferred developers and couplers include the following bicyclic 5-6heteroaromatic keratin dyeing compounds with one ring junction nitrogenand having one or two extra heteroatoms:

(I) H-pyrrolo[1,2-b]pyridazine

(i) Preferred Developers

Preferred H-pyrrolo[1,2-b]pyridazine developers are compounds accordingto the following formulas:

wherein D² and D⁵ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E², E³, E⁴, E⁵, and E⁶ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of pyrrolo[1,2-b]pyridazine-5-amine,H-pyrrolo[1,2-b]pyridazine-3,5-diamine,H-pyrrolo[1,2-b]pyridazine-3,5-diamine,H-pyrrolo[1,2-b]pyridazine-3,5,7-triamine,5-amino-H-pyrrolo[1,2-b]pyridazine-3-ol,pyrrolo[1,2-b]pyridazine-7-amine,H-pyrrolo[1,2-b]pyridazine-6,7-diamine,7-amino-H-pyrrolo[1,2-b]pyridazine-6-ol,H-pyrrolo[1,2-b]pyridazine-3,7-diamine, and7-amino-H-pyrrolo[1,2-b]pyridazine-3-ol.

(ii) Preferred Couplers

Preferred H-pyrrolo[1,2-b]pyridazine couplers are compounds according tothe following formulas:

wherein D² and D⁵ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E², E³, E⁴, E⁵ and E⁶ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of H-pyrrolo[1,2-b]pyridazin-3-amine,H-pyrrolo[1,2-b]pyridazin-3-ol, H-pyrrolo[1,2-b]pyridazin-6-amine,H-pyrrolo[1,2-b]pyridazin-6-ol, H-pyrrolo[1,2-b]pyridazin-3,6-diamine,and H-pyrrolo[1,2-b]pyridazin-3,6-diol.

(II) H-pyrrolo[1,2-f]pyrimidine

(i) Preferred Developers

Preferred H-pyrrolo[1,2-f]pyrimidine developers are compounds accordingto the following formulas:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E², E³, E⁴, E⁵ and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula IIa is selected from thegroup consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred developers of the present invention are selectedfrom the group consisting of pyrrolo[1,2-c]pyrimidine-5-amin,eH-pyrrolo[1,2-f]pyrimidine-1,5-diamine,H-pyrrolo[1,2-f]pyrimidine-3,5-diamine,H-pyrrolo[1,2-f]pyrimidine-1,3,5-triamine,H-pyrrolo[1,2-f]pyrimidine-3,5,7-triamine,H-pyrrolo[1,2-f]pyrimidine-1,5,7-triamine,H-pyrrolo[1,2-f]pyrimidine-1,3,5,7-tetraamine,5-amino-H-pyrrolo[1,2-f]pyrimidine-1-ol,5-amino-H-pyrrolo[1,2-f]pyrimidine-3-ol,5-amino-H-pyrrolo[1,2-f]pyrimidine-1,3-diol,H-pyrrolo[1,2-f]pyrimidine-6,7-diamine,7-amino-H-pyrrolo[1,2-f]pyrimidine-6-ol,pyrrolo[1,2-c]pyrimidine-7-amin, H-pyrrolo[1,2-f]pyrimidine-1,7-diamine,H-pyrrolo[1,2-f]pyrimidine-3,7-diamine,7-amino-H-pyrrolo[1,2-f]pyrimidine-1-ol,7-amino-H-pyrrolo[1,2-f]pyrimidine-3-ol,7-amino-H-pyrrolo[1,2-f]pyrimidine-1,3-diol,H-pyrrolo[1,2-f]pyrimidine-1,3,7-triamine, andH-pyrrolo[1,2-f]pyrimidine-1,5,7-triamine.

(ii) Preferred Couplers

Preferred H-pyrrolo[1,2-f]pyrimidine couplers are compounds according tothe following formulas:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E², E³, E⁴, E⁵ and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamido, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula IIc is selected from thegroup consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred couplers of the present invention are selected fromthe group consisting of H-pyrrolo[1,2-f]pyrimidin-1-amine,H-pyrrolo[1,2-f]pyrimidin-3-amine,H-pyrrolo[1,2-f]pyrimidin-1,3-diamine, H-pyrrolo[1,2-f]pyrimidin-1-ol,H-pyrrolo[1,2-f]pyrimidin-3-ol, H-pyrrolo[1,2-f]pyrimidin-1,3-diol,H-pyrrolo[1,2-f]pyrimidin-6-amine, H-pyrrolo[1,2-f]pyrimidin-6-ol,H-pyrrolo[1,2-f]pyrimidin-1,6-diamine,H-pyrrolo[1,2-f]pyrimidin-3,6-diamine,H-pyrrolo[1,2-f]pyrimidin-1,6-diol, andH-pyrrolo[1,2-f]pyrimidin-3,6-diol.

(III) H-pyrrolo[1,2-a]pyrazine

(i) Preferred Developers

Preferred H-pyrrolo[1,2-a]pyrazine developers are compounds according tothe following formulas:

wherein D² and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E², E³, E⁴, E⁶ and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of pyrrolo[1,2-a]pyrazin-8-ylamine,H-pyrrolo[1,2-a]pyrazine-1,5-diamine,H-pyrrolo[1,2-a]pyrazine-3,5-diamine,H-pyrrolo[1,2-a]pyrazine-1,5,7-triamine,5-amino-H-pyrrolo[1,2-a]pyrazine-1-ol, pyrrolo[1,2-a]pyrazin-6-ylamine,H-pyrrolo[1,2-a]pyrazine-6,7-diamine,7-amino-H-pyrrolo[1,2-a]pyrazine-6-ol,H-pyrrolo[1,2-a]pyrazine-1,7-diamine,7-amino-H-pyrrolo[1,2-a]pyrazine-1-ol, andH-pyrrolo[1,2-a]pyrazine-1,5,7-triamine.

(ii) Preferred Couplers

Preferred H-pyrrolo[1,2-a]pyrazine couplers are compounds according tothe following formulas:

wherein D² and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E², E³, E⁴, E⁶ and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of H-pyrrolo[1,2-a]pyrazin-1-amine,H-pyrrolo[1,2-a]pyrazin-1-ol, H-pyrrolo[1,2-a]pyrazin-6-amine,H-pyrrolo[1,2-a]pyrazin-6-ol, H-pyrrolo[1,2-a]pyrazin-1,6-diamine, andH-pyrrolo[1,2-a]pyrazin-1,6-diol.

(IV) H-pyrrolo[1,2-a]pyrimidine,

(i) Preferred Developers

Preferred H-pyrrolo[1,2-a]pyrimidine developers are compounds accordingto the following formulas:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E², E³, E⁴, E⁵ and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula IVa is selected from thegroup consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred developers of the present invention are selectedfrom the group consisting of pyrrolo[1,2-a]pyrimidin-8-ylamine,H-pyrrolo[1,2-a]pyrimidine-1,5-diamine,H-pyrrolo[1,2-a]pyrimidine-3,5-diamine,H-pyrrolo[1,2-a]pyrimidine-1,3,5-triamine,H-pyrrolo[1,2-a]pyrimidine-3,5,7-triamine,H-pyrrolo[1,2-a]pyrimidine-1,5,7-triamine,H-pyrrolo[1,2-a]pyrimidine-1,3,5,7-tetraamine,5-amino-H-pyrrolo[1,2-a]pyrimidine-1-ol,5-amino-H-pyrrolo[1,2-a]pyrimidine-3-ol,5-amino-H-pyrrolo[1,2-a]pyrimidine-1,3-diol,pyrrolo[1,2-a]pyrimidin-6-ylamine,H-pyrrolo[1,2-a]pyrimidine-6,7-diamine,7-amino-H-pyrrolo[1,2-a]pyrimidine-6-ol,H-pyrrolo[1,2-a]pyrimidine-1,7-diamine,H-pyrrolo[1,2-a]pyrimidine-3,7-diamine,7-amino-H-pyrrolo[1,2-a]pyrimidine-1-ol,7-amino-H-pyrrolo[1,2-a]pyrimidine-3-ol,7-amino-H-pyrrolo[1,2-a]pyrimidine-1,3-diol,H-pyrrolo[1,2-a]pyrimidine-1,3,7-triamine, andH-pyrrolo[1,2-a]pyrimidine-1,5,7-triamine.

(ii) Preferred Couplers

Preferred H-pyrrolo[1,2-a]pyrimidine couplers are compounds according tothe following formulas:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E², E³, E⁴, E⁵ and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula IVc is selected from thegroup consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred couplers of the present invention are selected fromthe group consisting of H-pyrrolo[1,2-a]pyrimidin-1-amine,H-pyrrolo[1,2-a]pyrimidin-3-amine,H-pyrrolo[1,2-a]pyrimidin-1,3-diamine, H-pyrrolo[1,2-a]pyrimidin-1-ol,H-pyrrolo[1,2-a]pyrimidin-3-ol, H-pyrrolo[1,2-a]pyrimidin-1,3-diol,H-pyrrolo[1,2-a]pyrimidin-6-amine, H-pyrrolo[1,2-a]pyrimidin-6-ol,H-pyrrolo[1,2-a]pyrimidin-1,6-diamine,H-pyrrolo[1,2-a]pyrimidin-3,6-diamine,H-pyrrolo[1,2-a]pyrimidin-1,6-diol, andH-pyrrolo[1,2-a]pyrimidin-3,6-diol.

(V) H-imidazo[1,5-a]pyridine

(i) Preferred Developers

Preferred H-imidazo[1,5-a]pyridine developers of formula V are compoundsaccording to the following formulas:

wherein D⁵ and D⁷ are selected from the group consisting of amino,hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E³, E⁴, E⁵ E⁶, and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula Va is selected from thegroup consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,5-a]pyridin-1-ylamine,H-imidazo[1,5-a]pyridine-1,5-diamine,H-imidazo[1,5-a]pyridine-3,5-diamine,H-imidazo[1,5-a]pyridine-1,3,5-triamine,H-imidazo[1,5-a]pyridine-3,5,7-triamine,H-imidazo[1,5-a]pyridine-1,5,7-triamine,H-imidazo[1,5-a]pyridine-1,3,5,7-tetraamine,5-amino-H-imidazo[1,5-a]pyridine-1-ol,5-amino-H-imidazo[1,5-a]pyridine-3-ol,5-amino-H-imidazo[1,5-a]pyridine-1,3-diol,H-imidazo[1,5-a]pyridine-6,7-diamine,7-amino-H-imidazo[1,5-a]pyridine-6-ol, imidazo[1,5-a]pyridin-3-ylamine,H-imidazo[1,5-a]pyridine-1,7-diamine,H-imidazo[1,5-a]pyridine-3,7-diamine,7-amino-H-imidazo[1,5-a]pyridine-1-ol,7-amino-H-imidazo[1,5-a]pyridine-3-ol,7-amino-H-imidazo[1,5-a]pyridine-1,3-diol,H-imidazo[1,5-a]pyridine-1,3,7-triamine, andH-imidazo[1,5-a]pyridine-1,5,7-triamine.

(ii) Preferred Couplers

Preferred H-imidazo[1,5-a]pyridine couplers are compounds according tothe following formulas:

wherein D⁵ and D⁷ are selected from the group consisting of amino,hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E³, E⁴, E⁵ E⁶, and E⁷ are each independently selected fromthe group consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamidol, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula Vc is selected from thegroup consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred couplers of the present invention are selected fromthe group consisting of H-imidazo[1,5-a]pyridin-1-amine,H-imidazo[1,5-a]pyridin-3-amine, H-imidazo[1,5-a]pyridin-1,3-diamine,H-imidazo[1,5-a]pyridin-1-ol, H-imidazo[1,5-a]pyridin-3-ol,H-imidazo[1,5-a]pyridin-1,3-diol, H-imidazo[1,5-a]pyridin-6-amine,H-imidazo[1,5-a]pyridin-6-ol, H-imidazo[1,5-a]pyridin-1,6-diamine,H-imidazo[1,5-a]pyridin-3,6-diamine, H-imidazo[1,5-a]pyridin-1,6-diol,and H-imidazo[1,5-a]pyridin-3,6-diol.

(VI) pyrazolo[1,5-b]pyridazine

(i) Preferred Developers

Preferred H-pyrazolo[1,5-b]pyridazine developers of formula VI arecompounds according to the following formula:

wherein D⁵ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

-   -   wherein E², E⁴, and E⁶ are each independently selected from the        group consisting of hydrogen, chlorine, bromine, fluorine,        amino, hydroxyl, cyano, methyl, ethyl, isopropyl,        trifluoromethyl, N,N-dimethylamino, N,N-diethylamino,        N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,        N-hydroxymethylamino, N-hydroxypropylamino,        N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,        N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy,        propyloxy, benzyloxy, methoxymethyl, methoxyethyl,        methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,        acetamido, propionamidol, butyramido, acetyl, butyryl,        propionyl, phenoxy, methylthio, ethylthio, propylthio,        butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,        pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl,        imidazolyl, thiadiazolyl, phenyl, sulfonyl, sulphonamido, and        ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of pyrazolo[1,5-b]pyridazin-3-ylamine,H-pyrazolo[1,5-b]pyridazine-3,5-diamine, and5-amino-H-pyrazolo[1,5-b]pyridazine-3-ol.

(ii) Preferred Couplers

Preferred H-pyrazolo[1,5-b]pyridazine couplers are compounds accordingto the following formula:

wherein D⁵ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E², E⁴, and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of H-pyrazolo[1,5-b]pyridazin-3-amine,H-pyrazolo[1,5-b]pyridazin-3-ol, H-pyrazolo[1,5-b]pyridazin-3,6-diamine,and H-pyrazolo[1,5-b]pyridazin-3,6-diol.

(VII) pyrazolo[1,5-f]pyrimidine

(i) Preferred Developers

Preferred pyrazolo[1,5-f]pyrimidine developers are compounds accordingto the following formula:

wherein D⁵ and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E² and E⁴ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of pyrazolo[1,5-c]pyrimidin-3-ylamine,pyrazolo[1,5-f]pyrimidine-1,5-diamine,pyrazolo[1,5-f]pyrimidine-3,5-diamine,pyrazolo[1,5-f]pyrimidine-1,3,5-triamine,5-amino-pyrazolo[1,5-f]pyrimidine-1-ol,5-amino-pyrazolo[1,5-f]pyrimidine-3-ol, and5-amino-pyrazolo[1,5-f]pyrimidine-1,3-diol.

(ii) Preferred Couplers

Preferred Pyrazolo[1,5-f]pyrimidine couplers are compounds according tothe following formula:

wherein D⁵ and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E² and E⁴ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of pyrazolo[1,5-f]pyrimidin-1-amine,pyrazolo[1,5-f]pyrimidin-3-amine, pyrazolo[1,5-f]pyrimidin-1,3-diamine,pyrazolo[1,5-f]pyrimidin-1-ol, pyrazolo[1,5-f]pyrimidin-3-ol,pyrazolo[1,5-f]pyrimidin-1,3-diol, pyrazolo[1,5-f]pyrimidin-1,6-diamine,pyrazolo[1,5-f]pyrimidin-3,6-diamine, pyrazolo[1,5-f]pyrimidin-1,6-diol,and pyrazolo[1,5-f]pyrimidin-3,6-diol.

(VIII) pyrazolo[1,5-a]pyrazine

(i) Preferred Developers

Preferred pyrazolo[1,5-a]pyrazine developers are compounds according tothe following formula:

wherein D⁷ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E², E⁴, and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of pyrazolo[1,5-a]pyrazin-3-ylamine,pyrazolo[1,5-a]pyrazine-1,5-diamine, and5-amino-pyrazolo[1,5-a]pyrazine-1-ol.

(ii) Preferred Couplers

Preferred pyrazolo[1,5-a]pyrazine couplers are compounds according tothe following formula:

wherein D⁷ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E², E⁴, and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of Pyrazolo[1,5-a]pyrazin-1-amine,Pyrazolo[1,5-a]pyrazin-1-ol, Pyrazolo[1,5-a]pyrazin-1,6-diamine, andPyrazolo[1,5-a]pyrazin-1,6-diol.

(IX) imidazo[1,5-b]pyridazine

(i) Preferred Developers

Preferred imidazo[1,5-b]pyridazine developers are compounds according tothe following formulas:

wherein D⁵ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E³, E⁴, and E⁶ are each independently selected from thegroup consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamido, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,5-b]pyridazin-5-ylamine,imidazo[1,5-b]pyridazin-7-ylamine, imidazo[1,5-b]pyridazine-3,5-diamine,imidazo[1,5-b]pyridazine-3,5,7-triamine,5-amino-imidazo[1,5-b]pyridazine-3-ol,imidazo[1,5-b]pyridazine-3,7-diamine, and7-amino-imidazo[1,5-b]pyridazine-3-ol.

(ii) Preferred Couplers

Preferred imidazo[1,5-b]pyridazine couplers are compounds according tothe following formulas:

wherein D⁵ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E³, E⁴, and E⁶ are each independently selected from thegroup consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamido, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of imidazo[1,5-b]pyridazin-3-amine, andimidazo[1,5-b]pyridazin-3-ol.

(X) imidazo[1,5-f]pyrimidine

(i) Preferred Developers

Preferred imidazo[1,5-f]pyrimidine developers are compounds according tothe following formulas:

wherein D⁵ D⁷ are each independently selected from the group consistingof amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E³, and E⁴ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,5-c]pyrimidin-1-ylamine,imidazo[1,5-c]pyrimidin-3-ylamine, imidazo[1,5-f]pyrimidine-1,5-diamine,imidazo[1,5-f]pyrimidine-3,5-diamine,imidazo[1,5-f]pyrimidine-1,3,5-triamine,imidazo[1,5-f]pyrimidine-3,5,7-triamine,imidazo[1,5-f]pyrimidine-1,5,7-triamine,imidazo[1,5-f]pyrimidine-1,3,5,7-tetraamine,5-amino-imidazo[1,5-f]pyrimidine-1-ol,5-amino-imidazo[1,5-f]pyrimidine-3-ol,5-amino-imidazo[1,5-f]pyrimidine-1,3-diol,imidazo[1,5-f]pyrimidine-1,7-diamine,imidazo[1,5-f]pyrimidine-3,7-diamine,7-amino-imidazo[1,5-f]pyrimidine-1-ol,7-amino-imidazo[1,5-f]pyrimidine-3-ol,7-amino-imidazo[1,5-f]pyrimidine-1,3-diol,imidazo[1,5-f]pyrimidine-1,3,7-triamine, andimidazo[1,5-f]pyrimidine-1,5,7-triamine.

(ii) Preferred Couplers

Preferred imidazo[1,5-f]pyrimidine couplers are compounds according tothe following formulas:

wherein D⁵ D⁷ are each independently selected from the group consistingof amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E³, and E⁴ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of Imidazo[1,5-f]pyrimidin-1-amine,Imidazo[1,5-f]pyrimidin-3-amine, Imidazo[1,5-f]pyrimidin-1,3-diamine,Imidazo[1,5-f]pyrimidin-1-ol, Imidazo[1,5-f]pyrimidin-3-ol, andImidazo[1,5-f]pyrimidin-1,3-diol.

(XI) imidazo[1,5-a]pyrazine

(i) Preferred Developers

Preferred imidazo[1,5-a]pyrazine developers are compounds according tothe following formulas:

wherein D⁷ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E³, E⁴, and E⁶ are each independently selected from thegroup consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamido, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,5-a]pyrazin-1-ylamine,imidazo[1,5-a]pyrazin-3-ylamine, imidazo[1,5-a]pyrazine-1,5-diamine,imidazo[1,5-a]pyrazine-1,5,7-triamine,5-amino-imidazo[1,5-a]pyrazine-1-ol, imidazo[1,5-a]pyrazine-1,7-diamine,7-amino-imidazo[1,5-a]pyrazine-1-ol, andimidazo[1,5-a]pyrazine-1,5,7-triamine.

(ii) Preferred Couplers

Preferred imidazo[1,5-a]pyrazine couplers are compounds according to thefollowing formulas:

wherein D⁷ is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E¹, E³, E⁴, and E⁶ are each independently selected from thegroup consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamido, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of imidazo[1,5-a]pyrazin-1-amine, andimidazo[1,5-a]pyrazin-1-ol.

(XII) imidazo[1,5-a]pyrimidine

(i) Preferred Developers

Preferred imidazo[1,5-a]pyrimidine developers are compounds according tothe following formulas:

wherein D⁵ and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E³, and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,5-a]pyrimidin-8-ylamine,imidazo[1,5-a]pyrimidin-6-ylamine, imidazo[1,5-a]pyrimidine-1,5-diamine,imidazo[1,5-a]pyrimidine-3,5 -diamine,imidazo[1,5-a]pyrimidine-1,3,5-triamine,imidazo[1,5-a]pyrimidine-3,5,7-triamine,imidazo[1,5-a]pyrimidine-1,5,7-triamine,imidazo[1,5-a]pyrimidine-1,3,5,7-tetraamine,5-amino-imidazo[1,5-a]pyrimidine-1-ol,5-amino-imidazo[1,5-a]pyrimidine-3-ol,5-amino-imidazo[1,5-a]pyrimidine-1,3-diol,imidazo[1,5-a]pyrimidine-1,7-diamine,imidazo[1,5-a]pyrimidine-3,7-diamine,7-amino-imidazo[1,5-a]pyrimidine-1-ol,7-amino-imidazo[1,5-a]pyrimidine-3-ol,7-amino-imidazo[1,5-a]pyrimidine-1,3-diol, imidazo[1,5-a]pyrimidine-1,3,7-triamine, andimidazo[1,5-a]pyrimidine-1,5,7-triamine.

(ii) Preferred Couplers

Preferred imidazo[1,5-a]pyrimidine couplers are compounds according tothe following formulas:

wherein D⁵ and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E¹, E³, and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of imidazo[1,5-a]pyrimidin-1-amine,imidazo[1,5-a]pyrimidin-3-amine, imidazo[1,5-a]pyrimidin-1,3-diamine,imidazo[1,5-a]pyrimidin-1-ol, imidazo[1,5-a]pyrimidin-3-ol, andimidazo[1,5-a]pyrimidin-1,3-diol.

(XII) imidazo[1,2-b]pyridazine

(i) Preferred Developers

Preferred imidazo[1,2-b]pyridazine developers are compounds according tothe following formula:

wherein D² and D⁵ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E⁴ and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,2-b]pyridazin-3-ylamine,imidazo[1,2-b]pyridazine-6,7-diamine,7-amino-imidazo[1,2-b]pyridazine-6-ol,imidazo[1,2-b]pyridazine-3,7-diamine,7-amino-imidazo[1,2-b]pyridazine-3-ol,imidazo[1,2-b]pyridazine-3,6,7-triamine,7-amino-imidazo[1,2-b]pyridazine-3,6-diol, and3,7-diamino-imidazo[1,2-b]pyridazine-6-ol.

(ii) Preferred Couplers

Preferred imidazo[1,2-b]pyridazine couplers are compounds according tothe following formula:

wherein D² and D⁵ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E⁴ and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of imidazo[1,2-b]pyridazin-3-amine,imidazo[1,2-b]pyridazin-3-ol, imidazo[1,2-b]pyridazin-6-amine,imidazo[1,2-b]pyridazin-6-ol, imidazo[1,2-b]pyridazin-3,6-diamine, andimidazo[1,2-b]pyridazin-3,6-diol.

(XIV) imidazo[1,2-f]pyrimidine

(i) Preferred Developers

Preferred imidazo[1,2-f]pyrimidine developers are compounds according tothe following formula:

wherein D² D⁵, and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E⁴ is selected from the group consisting of hydrogen, chlorine,bromine, fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,2-c]pyrimidin-3-ylamine,imidazo[1,2-f]pyrimidine-6,7-diamine,7-amino-imidazo[1,2-f]pyrimidine-6-ol,imidazo[1,2-f]pyrimidine-1,7-diamine,imidazo[1,2-f]pyrimidine-3,7-diamine,7-amino-imidazo[1,2-f]pyrimidine-1-ol,7-amino-imidazo[1,2-f]pyrimidine-3-ol,7-amino-imidazo[1,2-f]pyrimidine-1,3-diol,imidazo[1,2-f]pyrimidine-1,3,7-triamine,imidazo[1,2-f]pyrimidine-1,3,6,7-tetraamine, and7-amino-imidazo[1,2-f]pyrimidine-1,3,5-triol.

(ii) Preferred Couplers

Preferred Imidazo[1,2-f]pyrimidine couplers are compounds according tothe following formula:

wherein D² D⁵, and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E⁴ is selected from the group consisting of hydrogen, chlorine,bromine, fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of imidazo[1,2-f]pyrimidin-1-amine,imidazo[1,2-f]pyrimidin-3-amine, imidazo[1,2-f]pyrimidin-1,3-diamine,imidazo[1,2-f]pyrimidin-1-ol, imidazo[1,2-f]pyrimidin-3-ol,imidazo[1,2-f]pyrimidin-1,3-diol, imidazo[1,2-f]pyrimidin-6-amine,imidazo[1,2-f]pyrimidin-6-ol, imidazo[1,2-f]pyrimidin-1,6-diamine,imidazo[1,2-f]pyrimidin-3,6-diamine, imidazo[1,2-f]pyrimidin-1,6-diol,imidazo[1,2-f]pyrimidin-3,6-diol, imidazo[1,2-f]pyrimidin-1,3,6-triol,imidazo[1,2-f]pyrimidin-1,3,6-triamine, and3,6-diamino-imidazo[1,2-f]pyrimidin-1-ol.

(XV) imidazo[1,2-a]pyrazine

(i) Preferred Developers

Preferred imidazo[1,2-a]pyrazine developers are compounds according tothe following formula:

wherein D² and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E⁴ and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,2-a]pyrazin-3-ylamine,imidazo[1,2-a]pyrazine-6,7-diamine, 7-amino-imidazo[1,2-a]pyrazine-6-ol,imidazo[1,2-a]pyrazine-1,7-diamine, 7-amino-imidazo[1,2-a]pyrazine-1-ol,imidazo[1,2-a]pyrazine-1,6,7-triamine,imidazo[1,2-a]pyrazine-1,2,6,7-tetramine,imidazo[1,2-a]pyrazine-1,4,6,7-tetramine,7-amino-imidazo[1,2-a]pyrazine-1,6-diol,7-amino-imidazo[1,2-a]pyrazine-1,4,6-triol, and7-amino-imidazo[1,2-a]pyrazine-1,2,6-triol.

(ii) Preferred Couplers

Preferred Imidazo[1,2-a]pyrazine couplers are compounds according to thefollowing formula:

wherein D² and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl;

wherein E⁴ and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.

Especially preferred couplers of the present invention are selected fromthe group consisting of imidazo[1,2-a]pyrazin-1-amine,imidazo[1,2-a]pyrazin-1-ol, imidazo[1,2-a]pyrazin-6-amine,imidazo[1,2-a]pyrazin-6-ol, imidazo[1,2-a]pyrazin-1,6-diamine,imidazo[1,2-a]pyrazin-1,6-diol, imidazo[1,2-a]pyrazin-1,2,6-triol,imidazo[1,2-a]pyrazin-1,2,6-triamine, imidazo[1,2-a]pyrazin-1,4,6-triol,imidazo[1,2-a]pyrazin-1,4,6-triamine,imidazo[1,2-a]pyrazin-1,2,4,6-tetraamine, andimidazo[1,2-a]pyrazin-1,2,4,6-tetraol.

(XVI) imidazo[1,2-a]pyrimidine

(i) Preferred Developers

Preferred Imidazo[1,2-a]pyrimidine developers are compounds according tothe following formula:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E⁵ E⁶, and E⁷ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula XVIa is selected fromthe group consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred developers of the present invention are selectedfrom the group consisting of imidazo[1,2-a]pyrimidin-3-ylamine,7-amino-imidazo[1,2-a]pyrimidine-1,3-diol,imidazo[1,2-a]pyrimidine-1,3,7-triamine,imidazo[1,2-a]pyrimidine-1,5,7-triamine,imidazo[1,2-a]pyrimidine-1,6,7-triamine,imidazo[1,2-a]pyrimidine-3,6,7-triamine,7-amino-imidazo[1,2-a]pyrimidine-1,6-diol,7-amino-imidazo[1,2-a]pyrimidine-3,6-diol,7-amino-imidazo[1,2-a]pyrimidine-1,3,6-triol, andimidazo[1,2-a]pyrimidine-1,3,6,7-tetraamine.

(ii) Preferred Couplers

Preferred Imidazo[1,2-a]pyrimidine couplers are compounds according tothe following formula:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiadiazolyl;

wherein E⁵ E⁶, and E⁷ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido;

wherein at least one of the E⁵ or E⁷ in formula XVIb is selected fromthe group consisting of amino, hydroxyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.

Especially preferred couplers of the present invention are selected fromthe group consisting of Imidazo[1,2-a]pyrimidin-1,6-diamine,Imidazo[1,2-a]pyrimidin-3,6-diamine, Imidazo[1,2-a]pyrimidin-1,6-diol,Imidazo[1,2-a]pyrimidin-3,6-diol,Imidazo[1,2-a]pyrimidin-1,3,6-triamine,Imidazo[1,2-a]pyrimidin-1,3,6-triol,6-amino-Imidazo[1,2-a]pyrimidin-1,3-diol, and1,3-diamino-Imidazo[1,2-a]pyrimidin-6-ol.

SYNTHESIS EXAMPLES

The following are non-limiting synthesis examples of the presentinvention.

Example A 7-Hydroxyimidazo[1,5-c]pyrimidin-5(6H)-one, Obtainable fromthe Following Synthesis Strategy

Reaction of 6-(chloromethyl)uracil (CAS 18592-13-7) with ammonia givescompound 1 (J. Heterocycl. Chem., 1986, 23, 981). Reaction of compound 1with formic acid affords compound 2 (J. Heterocycl. Chem., 1986, 23,981). Dehydration of compound 2 with polyphosphoric acid, or sulfuricacid, or with acetic anhydride leads to7-hydroxyimidazo[1,5-c]pyrimidin-5(6H)-one 1-1.

Example B 7-Hydroxy-3-methylimidazo[1,5-c]pyrimidin-5(6H)-one,Obtainable from the Following Synthesis Strategy

Reaction of 6-(chloromethyl)uracil (CAS 18592-13-7) with ammonia givescompound 1 (J. Heterocycl. Chem., 1986, 23, 981). Reaction of compound 1with acetic anhydride affords compound 2 (J. Heterocycl. Chem., 1986,23, 981). Dehydration of compound 2 with polyphosphoric acid, orsulfuric acid, or with acetic anhydride leads to7-hydroxy-3-methylimidazo[1,5-c]pyrimidin-5(6H)-one 1-2.

Example C Imidazo[1,2-a]pyrimidine-5,7-diol, Obtainable from theFollowing Synthesis Strategy

Reaction of 2-aminoimidazole sulfate (CAS 1450-93-7) with diethylmalonate (CAS 105-53-3) gives compound 1 (J. Het. Chem., 1973, 10,1021). Thermolysis of compound 1 leads toimidazo[1,2-a]pyrimidine-5,7-diol 3-1 (J. Het. Chem., 1973, 10, 1021).

Example D Imidazo[1,2-a]pyrimidin-5,7-diamine, Obtainable from theFollowing Synthesis Strategy

Reaction of 2-aminoimidazole sulfate (CAS 1450-93-7) with diethylmalonate (CAS 105-53-3) gives compound 1 (J. Het. Chem., 1973, 10,1021). Thermolysis of compound 1 leads to compound 2 (J. Het. Chem.,1973, 10, 1021). Reaction of compound 2 with phosphorus oxychlorideaffords compound 3 (J. Med. Chem., 1975, 18, 1253). Reaction of compound3 with ammonia gives imidazo[1,2-a]pyrimidin-5,7-amine 3-2.

Example E 2-Methylimidazo[1,2-c]pyrimidine-3,5,7-triamine, Obtainablefrom the Following Synthesis Strategy

Reaction of 2,4,6-triaminopyrimidine (CAS 1004-38-2) with ethyl2-chloroacetoacetate (CAS 609-15-4) in dimethylformamide gives compound1 (J. Org. Chem., 1999, 64, 634). Reaction of compound 1 with sodiumhydroxide leads to compound 2 (see similar process in Farmaco Ed. Sci.,1991, 46, 1099). Treatment of acid 2 with diphenylphosphoryl azide (CAS26386-88-9) in the presence of tert-butanol gives carbamate 3 (seesimilar procedure in J. Med. Chem., 1991, 34, 1594). Hydrolysis ofcarbamate 3 with hydrochloric acid provides2-methylimidazo[1,2-c]pyrimidine-3,5,7-triamine 8-1 (see similarprocedure in Tetr. Lett, 1999, 40, 721).II. Keratin Dyeing Composition Components

The inventive compositions for the oxidative dyeing of keratin fiberscomprise the hair-dyeing compound described above in the hair-dyeingcompounds section and a medium suitable for dyeing. The inventivecompositions may further comprise additional components known,conventionally used, or otherwise effective for use in oxidative dyecompositions, including but limited to: developer dye compounds; couplerdye compounds; direct dyes; oxidizing agents; thickeners; chelants; pHmodifiers and buffering agents; carbonate ion sources and radicalscavenger systems; anionic, cationic, nonionic, amphoteric orzwitterionic surfactants, or mixtures thereof; anionic, cationic,nonionic, amphoteric or zwitterionic polymers, or mixtures thereof;fragrances; buffers; dispersing agents; peroxide stabilizing agents;natural ingredients, e.g. proteins and protein derivatives, and plantmaterials (e.g. aloe, chamomile and henna extracts); silicones (volatileor non-volatile, modified or non-modified), film-forming agents,ceramides, preserving agents; and opacifiers.

Some adjuvants referred to above, but not specifically described below,which are suitable are listed in the International Cosmetics IngredientDictionary and Handbook, (8^(th) ed.; The Cosmetics, Toiletry, andFragrance Association). Particularly, vol. 2, sections 3 (ChemicalClasses) and 4 (Functions) are useful in identifying specific adjuvantsto achieve a particular purpose or multipurpose.

A. Medium Suitable for Dyeing

The medium suitable for dyeing may be selected from water, or a mixtureof water and at least one organic solvent to dissolve the compounds thatwould not typically be sufficiently soluble in water. Suitable organicsolvents for use herein include, but are not limited to: C1 to C4 loweralkanols (e.g., ethanol, propanol, isopropanol), aromatic alcohols (e.g.benzyl alcohol and phenoxyethanol); polyols and polyol ethers (e.g.,carbitols, 2-butoxyethanol, propylene glycol, propylene glycolmonomethyl ether, diethylene glycol monoethyl ether, monomethyl ether,hexylene glycol, glycerol, ethoxy glycol), and propylene carbonate. Whenpresent, organic solvents are typically present in an amount rangingfrom 1% to 30%, by weight, of the composition. Preferred solvents arewater, ethanol, propanol, isopropanol, glycerol, 1,2-propylene glycol,hexylene glycol, ethoxy diglycol, and mixtures thereof. Additionalmediums suitable for dyeing may include oxidizing agents as describedbelow.

B. Auxiliary Developers

Suitable developers for use in the compositions described hereininclude, but are not limited to p-phenylenediamine derivatives, e.g.benzene-1,4-diamine (commonly known as p-phenylenediamine),2-methyl-benzene-1,4-diamine, 2-chloro-benzene-1,4-diamine,N-phenyl-benzene-1,4-diamine, N-(2-ethoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known asN,N-bis(2-hydroxyethyl)-p-phenylenediamine)(2,5-diamino-phenyl)-methanol, 1-(2′-Hydroxyethyl)-2,5-diaminobenzene,2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine,2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,N⁴,N⁴,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine,1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine,N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine,2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-1,4-diamine,1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1,4-diamine,2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,N,N-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol,2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,N-(2-methoxyethyl)-benzene-1,4-diamine,3-[(4-aminophenyl)amino]propan-1-ol,3-[(4-aminophenyl)-amino]propane-1,2-diol,N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; p-aminophenol derivativessuch as: 4-amino-phenol (commonly known as p-aminophenol),4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,4-amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene,4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol,4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol,4-amino-2-fluoro-phenol; 1-Hydroxy-2,4-diaminobenzene;1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene; 2,4-Diamino-5-methylphenetol;o-phenylenediamine derivatives such as: 3,4-Diaminobenzoic acid andsalts thereof; o-aminophenol derivatives such as: 2-amino-phenol(commonly known as o-aminophenol), 2,4-diaminophenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; andheterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonlyknown as 2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,N²,N²-dimethyl-pyridine-2,5-diamine,2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol,6-methoxy-N²-methyl-pyridine-2,3-diamine,2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine,pyrazolo[1,5-a]-pyrimidine-3,7-diamine,5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2,5,6,7-teramethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2-methylpyrazolo[1,5-a]pyrimidin-3,7-diamine hydrochloride;4-Hydroxy-2,5,6-triaminopyrimidine;1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and1-Hydroxyethyl-4,5-diaminopyrazole sulphate.

Additional developers are selected from the group consisting ofN-(3-furylmethyl)benzene-1,4-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(2-furylmethyl)benzene-1,4-diamine;N-Thiophen-2-ylmethyl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]1,4-diamine;2-(6-Methyl-pyridin-2-yl)-benzene-1,4-diamine;2-Pyridin-2-yl-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-Thiazol-2-yl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide; 3′-Fluoro-biphenyl-2,5-diamine;2-Propenyl-benzene-1,4-diamine; 2′-Chloro-biphenyl-2,5-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(3-furylmethyl)benzene-1,4-diamine; 4′-Methoxy-biphenyl-2,5-diamine;N-(4-Amino-benzyl)-benzene-1,4-diamine;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4′-triaminehydrochloride; 5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diaminehydrochloride; 5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;4-Amino-2-propylaminomethyl-phenol; hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide;hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride hydrochloride;5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride;2′,4′-Diamino-biphenyl-4-ol; hydrochloride;5-Cyclobutylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol;hydrochloride; 2′,4′-Diamino-biphenyl-4-ol hydrochloride;Biphenyl-2,4,4′-triamine;5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamidehydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride;4-Amino-2-(isopropylamino-methyl)-phenol hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol hydrochloride;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol; and5-Cyclobutylamino-2-methyl-phenol.

Preferred developers include but are not limited to: p-phenylenediaminederivatives such as: 2-methyl-benzene-1,4-diamine; benzene-1,4-diamine;1-(2,5-diamino-phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol;N-(2-methoxyethyl)benzene-1,4-diamine;2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;1-(2,5-diaminophenyl)ethane-1,2-diol;1-(2′-Hydroxyethyl)-2,5-diaminobenzene;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; and mixtures thereof;p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino-phenol,4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol;1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;1-Hydroxy-2,4-diaminobenzene; 1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene;4-Amino-2-aminomethylphenol; 2,4-Diamino-5-methylphenetol;4-Amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene;1-methoxy-2-amino-4-(2′hydroxyethylamino)benzene; 5-aminosalicylic acidand salts thereof; and mixtures thereof; o-phenylenediamine derivativessuch as: 3,4-Diaminobenzoic acid and salts thereof; o-aminophenolderivatives such as: 2-amino-phenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide;2-amino-4-methyl-phenol; and mixtures thereof; and heterocyclicderivatives such as: pyrimidine-2,4,5,6-tetramine;1-methyl-1H-pyrazole-4,5-diamine;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol;1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine;1-(benzyl)-1H-pyrazole-4,5-diamine; N²,N²-dimethyl-pyridine-2,5-diamine;4-Hydroxy-2,5,6-triaminopyrimidine;1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and mixtures thereof.

More preferred developers include: 2-methyl-benzene-1,4-diamine;benzene-1,4-diamine; N,N-Bis(2-hydroxyethyl)-p-phenylenediamine;4-amino-phenol; 4-methylamino-phenol; 4-amino-3-methyl-phenol;1-Hydroxy-2,4-diaminobenzene; 2-amino-phenol; 2-amino-5-methyl-phenol;2-amino-6-methyl-phenol; 1-methyl-1H-pyrazole-4,5-diamine;1-Hydroxyethyl-4,5-diaminopyrazole sulphate;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol; and mixtures thereof.

C. Auxiliary Couplers

Suitable couplers for use in the compositions described herein include,but are not limited to: phenols, resorcinol and naphthol derivativessuch as: naphthalene-1,7-diol, benzene-1,3-diol,4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol,2-methyl-benzene-1,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonicacid, 2-isopropyl-5-methylphenol,1,2,3,4-tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol,4-hydroxy-naphthalene-1-sulfonic acid, benzene-1,2,3-triol,naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-diol,4,6-dichlorobenzene-1,3-diol, 2,3-dihydroxy-[1,4]naphthoquinone; and1-Acetoxy-2-methylnaphthalene; m-phenylenediamines such as:2,4-diaminophenol, benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol,2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-methyl-benzene-1,3-diamine,2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(2,4-diamino-phenyl)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-aceticacid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,4-ethoxy-6-methyl-benzene-1,3-diamine,2-(2,4-diamino-5-methyl-phenoxy)-ethanol,4,6-dimethoxy-benzene-1,3-diamine,2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,3-(2,4-diamino-phenoxy)-propan-1-ol, N-[3-(dimethylamino)phenyl]urea,4-methoxy-6-methylbenzene-1,3-diamine,4-fluoro-6-methylbenzene-1,3-diamine,2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,3-(2,4-diaminophenoxy)-propane-1,2-diol,2-[2-amino-4-(methylamino)-phenoxy]ethanol,2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-[(3-aminophenyl)amino]ethanol,2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;N-(2-aminoethyl)benzene-1,3-diamine,4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine,1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and2,4-dimethoxybenzene-1,3-diamine; m-aminophenols such as:3-amino-phenol, 2-(3-hydroxy4-methyl-phenylamino)-acetamide,2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,5-amino-2-(2-hydroxy-ethoxy)-phenol,2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,5-amino4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,5-amino4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol,3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,5-[(3-hydroxy-propyl)amino]-2-methylphenol,3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol,3-[(2-hydroxyethyl)amino]-2-methylphenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)amino-benzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene; and heterocyclic derivativessuch as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,1,3-benzodioxol-5-amine,2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,1H-indol4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,6-bromo-1,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-2,6-diamine,3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol, 1H-indole-2,3-dione,indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine,6-methoxypyridine-2,3-diamine; 3,4-dihydro-2H-1,4-benzoxazin-6-amine;4-hydroxy-N-methylindole, 1H-5-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole, 2,6-dihydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 5-methylpyrazolo[5,1-e]-1,2,3-triazole, 5-methyl-6-chloropyrazolo[5,1-e]-1,2,3,-triazole,5-phenylpyrazolo[5,1-e]-1,2,3-triazole and its addition salts,1H-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole tosylate,7,8-dicyano4-methylimidazolo-[3,2-a]imidazole,2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one,2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-one, and2-methyl-5-methoxymethyl-pyrazolo[1,5-a]pyrimidin-7-one;6-Hydroxybenzomorpholine; and 3-Amino-2-methylamino-6-methoxypyridine;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one.

Additional couplers are selected from the group consisting ofN-(3-furylmethyl)benzene-1,4-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(2-furylmethyl)benzene-1,4-diamine;N-Thiophen-2-ylmethyl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]1,4-diamine;2-(6-Methyl-pyridin-2-yl)-benzene-1,4-diamine;2-Pyridin-2-yl-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-Thiazol-2-yl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide; 3′-Fluoro-biphenyl-2,5-diamine;2-Propenyl-benzene-1,4-diamine; 2′-Chloro-biphenyl-2,5-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(3-furylmethyl)benzene-1,4-diamine; 4′-Methoxy-biphenyl-2,5-diamine;N-(4-Amino-benzyl)-benzene-1,4-diamine;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4′-triaminehydrochloride; 5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diaminehydrochloride; 5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;4-Amino-2-propylaminomethyl-phenol; hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide;hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride hydrochloride;5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride;2′,4′-Diamino-biphenyl-4-ol; hydrochloride;5-Cyclobutylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol;hydrochloride; 2′,4′-Diamino-biphenyl-4-ol hydrochloride;Biphenyl-2,4,4′-triamine;5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamidehydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride;4-Amino-2-(isopropylamino-methyl)-phenol hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol hydrochloride;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol; and5-Cyclobutylamino-2-methyl-phenol.

Preferred couplers include but are not limited to: phenol, resorcinol,and naphthol derivatives such as: naphthalene-1,7-diol,benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol,2-methyl-naphthalen-1-ol, naphthalene-1,5-diol, naphthalene-2,7-diol,benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and2-isopropyl-5-methylphenol; 1,2,4-Trihydroxybenzene;1-Acetoxy-2-methylnaphthalene; and mixtures thereof; m-phenylenediaminederivatives such as: benzene-1,3-diamine,2-(2,4-diamino-phenoxy)-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;2,4-Diamino-5-fluorotoluenesulfatehydrate;1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and mixtures thereof;m-aminophenol derivatives such as: 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, and3-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;1-Hydroxy-3-amino-2,4-dichlorobenzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene;5-Amino-4-chloro-2-methylphenol; and mixtures thereof; and heterocyclicderivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,3-benzodioxol-5-ol,1,3-benzodioxol-5-amine, 1H-indol-4-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 1H-indole-2,3-dione,pyridine-2,6-diamine, 2-aminopyridin-3-ol, 4-hydroxy-N-methylindole,1H-5-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 6-Hydroxybenzomorpholine;2,6-Dihydroxy-3,4-dimethylpyridine; 3,5-Diamino-2,6-dimethoxypyridine;3-Amino-2-methylamino-6-methoxypyridine;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

More preferred couplers include: benzene-1,3-diol;4-chlorobenzene-1,3-diol; 2-methyl-benzene-1,3-diol;benzene-1,3-diamine; 3-amino-phenol; 5-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one; 2-aminopyridin-3-ol;1-phenyl-3-methylpyrazol-5-one;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

Additional preferred developers and couplers include5-methoxymethyl-2-aminophenol, 5-ethyl-2-aminophenol,5-phenyl-2-aminophenol, and 5-cyanoethyl-2-aminophenol.

Further preferred developers and couplers include:

5-membered heteroaromatic keratin dyeing compounds with one, two, orthree heteroatoms relating to the following compounds:

wherein Z is selected from the group consisting of S and O;

wherein Y is selected from the group consisting of NA¹, S and O;

Bicyclic fused 5-5 heteroaromatic keratin dyeing compounds with two orthree heteroatoms relating to the following compounds:

wherein Y and Z are independently selected from the group consisting ofNA¹, S and O;

Bicyclic 5-5 heteroaromatic compounds having a ring junction nitrogenaccording to the following formulas:

wherein Y is selected from the group consisting of S and O;

Tricyclic 5-6-5 heteroaromatic keratin dyeing compounds having twoheteroatoms according to the following formulas:

wherein Y and Z are selected from the group consisting of NA¹, S, and O;

Bicyclic 5-6 heteroaromatic keratin dyeing compounds with one ringjunction nitrogen and one or two extra heteroatoms according to thefollowing formulas:

Tricyclic fused 6-5-6 heteroaromatic keratin dyeing compounds having oneheteroatom according to the following formula:

wherein Y is independently selected from the group consisting of NA¹, Sand O;

5-membered aza heteroaromatic keratin dyeing compounds with an N-hydroxyor N-amino group and derivatives thereof, according to the followingformulas:

wherein B₁, B₂, B₃, and B₄ are selected from the group consisting of CHand N;

wherein the corresponding R¹, R², R³, and R⁴ is absent when B is N;

Bicyclic 5-6 systems of aza heteroaromatic keratin dyeing compoundswherein the 5-membered rings have one to three nitrogen atoms and anN-hydroxy or N-amino group and derivatives thereof, according to thefollowing formulas:

wherein B₁ and B₂ are independently selected from CH or N;

wherein the corresponding R¹ and R² is absent when B is N;

Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing compoundswith an N-hydroxy or N-amino group and derivatives thereof, according tothe following formulas:

Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing compoundshaving a ring junction nitrogen and an N-hydroxy or N-amino group andderivatives thereof, according to the following formulas:

Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing compoundshaving a ring junction nitrogen and an N-hydroxy or N-amino group andderivatives thereof, according to the following formulas:

wherein B₁, B₂, B₃, B₄, and B₅ are selected from the group consisting ofCH and N;wherein the corresponding R1,R2, R3, R4, and R5 is absent when B is N;N-oxides of six-membered rings with one or two nitrogen atoms accordingto the following formulas:

Bicyclic 6-6 (0:1, 0:2, 1:1, 1:2) aza heteroaromatic keratin dyeingcompounds with one or two N-oxides, according to the following formulas:

Bicyclic 5-5 heteroaromatic compounds with a ring junction N (1:0, 1:1,2:0, 2:1), according to the following formulas:

wherein Y is selected from the group consisting of CH₂, NR⁷, O or S;

Bicyclic 5-5 (1:2) heteroaromatic N-oxide keratin dyeing compounds andderivatives thereof, according to the following formulas:

wherein Y and Z are selected from the group consisting of NR⁵, O and S;Mono N-oxide derivatives of 5-membered heteroaromatic compounds andderivatives thereof, according to the following formulas:

wherein Y is O, NR⁵ or S;Mono- or di- N-oxide derivatives of bicyclic 5-6 (2:0, 3:0, 2:1, 3:1)heteroaromatic compounds and derivatives thereof, according to thefollowing formulas:

wherein Y is selected from the group consisting of NR⁸, O or S;

N-oxide derivatives of bicyclic 5-6 heteroaromatic compounds with a ringjunction N (0:1, 1:0 & 1:1) and derivatives thereof, according to thefollowing formulas:

wherein all of the aforementioned R groups are the same or different andare selected from the group consisting of:

(a) C-linked monovalent substituents selected from the group consistingof:

-   -   (i) substituted or unsubstituted, straight or branched, alkyl,        mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems,    -   (ii) substituted or unsubstituted, mono- or poly-cyclic        aliphatic, aryl, or heterocyclic systems, and    -   (iii) substituted or unsubstituted, mono-, poly-, or per-fluoro        alkyl systems; wherein said systems of (i), (ii) and (iii)        comprise from about 1 to about 10 carbon atoms and from about 0        to about 5 heteroatoms selected from the group consisting of O,        S, N, P, and Si;    -   wherein substituents of the substituted systems of the C-linked        monovalent substituents are selected from the group consisting        of amino, hydroxyl, alkylamino (linear, branched, or cyclic        C1-C5), dialkylamino (linear, branched, or cyclic C1-C5),        hydroxyalkylamino (linear, branched, or cyclic C1-C5),        dihydroxyalkylamino (linear, branched, or cyclic C1-C5),        arylamino or substituted arylamino (substituents are halogen,        C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5        alkylamino), heteroarylamino or substituted heteroarylamino        (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,        trifluoromethyl, amino, C1-C5 alkylamino), arylmethylamino or        substituted arylmethylamino (substituents are halogen, C1-C5        alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),        and heteroarylmethylamino or substituted heteroarylmethylamino        (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,        trifluoromethyl, amino, C1-C5 alkylamino),

(b) S-linked monovalent substituents selected from the group consistingof SA¹, SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²;

(c) O-linked monovalent substituents selected from the group consistingof OA¹, and ONA¹A²;

(d) N-linked monovalent substituents selected from the group consistingof NA¹A², (NA¹A²A³)⁺, NA¹OA², NA¹SA², NO₂, N═NA¹, N═NOA¹, NA¹CN, andNA¹NA²A³;

(e) monovalent substituents selected from the group consisting of COOA¹,CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A², CN, and X;

(f) fluoroalkyl monovalent substituents selected from the groupconsisting of mono-, poly-, and per-fluoro alkyl systems comprising fromabout 1 to about 12 carbon atoms and from about 0 to about 4heteroatoms; and

(g) hydrogen,

wherein A¹, A², and A³ are monovalent and are independently selectedfrom the group consisting of: H; substituted or unsubstituted, straightor branched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,aliphatic, heteroaliphatic, or heteroolefinic systems; substituted orunsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclicsystems; and substituted or unsubstituted, mono-, poly-, or per-fluoroalkyl systems, or A¹ and A² together with nitrogen atoms to which theyare bound form a ring; wherein said systems comprise from about 1 toabout 10 carbon atoms and from about 0 to about 5 heteroatoms selectedfrom the group consisting of O, S, N, P, and Si;

wherein X is a halogen selected from the group consisting of F, Cl, Br,and I.

D. Direct Dyes

The inventive compositions may also comprise compatible direct dyes, inan amount sufficient to provide additional coloring, particularly withregard to intensity. Typically, such an amount will range from 0.05% to4%, by weight, of the composition. Suitable direct dyes include but arenot limited to: Acid Yellow 1, Acid Orange 3, Disperse Red 17, BasicBrown 17, Acid Black 52, Acid Black 1, Disperse Violet 4,4-Nitro-o-Phenylenediamine, 2-Nitro-p-Phenylenediamine, Picramic Acid,HC Red No. 13, 1,4-Bis-(2′-Hydroxyethyl)-amino-2-nitrobenzene, HC YellowNo. 5, HC Red No. 7, HC Blue No. 2, HC Yellow No. 4, HC Yellow No. 2, HCOrange No. 1, HC Red No. 1,2-Chloro-5-nitro-N-Hydroxyethyl-p-phenylenediamine, HC Red No. 3,4-Amino-3-nitrophenol, 2-Hydroxyethylamino-5-nitroanisole,3-nitro-p-Hydroxyethylaminophenol, 2-amino-3-nitrophenol,6-nitro-o-toluidine, 3-methylamino-4-nitrophenoxyethanol,2-nitro-5-glycerymethylanaline, HC Yellow No. 11, HC Violet No. 1, HCOrange No. 2, HC Orange No. 3, HC Yellow No. 9, 4-NitrophenylAminoethylurea, HC Red No. 10, HC Red No. 11, 2-Hydroxyethyl picramicacid, HC Blue No. 12, HC Yellow No. 6, Hydroxyethyl-2-nitro-p-toluidine,HC Yellow No. 12, HC Blue No. 10, HC Yellow No. 7, HC Yellow No. 10, HCBlue No. 9, N-ethyl-3-nitro PABA,4-amino-2-nitrophenyl-amine-2′-carboxylic acid,2-chloro-6-ethylamino-4-nitrophenol, 6-Nitro-2,5-pyridinediamine, HCViolet No. 2, 2-amino-6-chloro-4-nitrophenol,4-hydroxypropylamino-3-nitrophenol, HC Yellow No. 13,1,2,3,4-Tetrahydro-6-nitrochinoxalin, HC Red No. 14, HC Yellow No. 15,HC Yellow No. 14, 3-Amino-6-methylamino-2-nitropyridine,2,6-diamino-3-((pyridine-3-yl)azo)pyridine, Basic Red No. 118, BasicOrange No. 69, N-(2-nitro-4-aminophenyl)-allylamine,4-[(4-Amino-3-methylphenyl)(4-Imino-3-methyl-2,5-Cyclohexadien-1-ylidene)Methyl]-2-Methyl-benzeneamine-Hydrochloride,1H-Imidazolium,2-[[4-(dimethyl-amino)phenyl]azo]-1,3-dimethylchloride,Pyridinium, 1-methyl-4-[(methylphenyl-hydrazono)methyl]-, methylsulfate, 1H-Imidazolium, 2-[(4-aminophenyl)azo]-1,3-dimethyl, chloride,Basic Red 22, Basic Red 76, Basic Brown 16, Basic Yellow 57,7-(2′,4′-Dimethyl-5′-sulfophenylazo)-5-sulfo-8-hydroxynaphthalene, AcidOrange 7, Acid Red 33,1-(3′-Nitro-5′-sulfo-6′-oxophenylazo)-oxo-naphthalene chromium complex,Acid Yellow 23, Acid Blue 9, Basic Violet 14, Basic Blue 7, Basic Blue26, Sodium salt of mixture of mono- & disulfonic acids (mainly thelatter) of quinophthlanone or 2-quinolylindandione, Basic Red 2, BasicBlue 99, Disperse Red 15, Acid Violet 43, Disperse Violet 1, Acid Blue62, Pigment Blue 15, Acid Black 132, Basic Yellow 29, Disperse Black 9,1-(N-Methylmorpholinium-propylamino)-4-hydroxy-anthraquinonemethylsulfate, HC Blue No. 8, HC Red No. 8, HC Green No. 1, HC Red No.9, 2-Hydroxy-1,4-naphthoquinone, Acid Blue 199, Acid Blue 25, Acid Red4, Henna Red, Indigo, Cochenille, HC Blue 14, Disperse Blue 23, DisperseBlue 3, Violet 2, Disperse Blue 377, Basic Red 51, Basic Orange 31,Basic Yellow 87, and mixtures thereof. Preferred direct dyes include butare not limited to: Disperse Black 9, HC Yellow 2, HC Yellow 4, HCYellow 15, 4-nitro-o-phenylenediamine, 2-amino-6-chloro 4-nitrophenol,HC Red 3, Disperse Violet 1, HC Blue 2, Disperse Blue 3, Disperse Blue377, Basic Red 51, Basic Orange 31, Basic Yellow 87, and mixturesthereof.

E. Oxidizing Agent

The inventive compositions may comprise an oxidizing agent, present inan amount sufficient to bleach melanin pigment in hair and/or causeformation of dye chromophores from oxidative dye precursors (includingdevelopers and/or couplers when present). Typically, such an amountranges from 1% to 20%, preferably from 3% to 15%, more preferably from6% to 12%, by weight, of the developer composition. Inorganic peroxygenmaterials capable of yielding hydrogen peroxide in an aqueous medium arepreferred, and include but are not limited to: hydrogen peroxide;inorganic alkali metal peroxides (e.g. sodium periodate and sodiumperoxide); organic peroxides (e.g. urea peroxide, melamine peroxide);inorganic perhydrate salt bleaching compounds (e.g. alkali metal saltsof perborates, percarbonates, perphosphates, persilicates, andpersulphates, preferably sodium salts thereof), which may beincorporated as monohydrates, tetrahydrates, etc.; alkali metalbromates; enzymes; and mixtures thereof. Preferred is hydrogen peroxide.

F. Thickeners

The inventive compositions may comprise a thickener in an amountsufficient to provide the composition with a viscosity so that it can bereadily applied to the hair without unduly dripping off the hair andcausing mess. Typically, such an amount will be at least 0.1%,preferably at least 0.5%, more preferably, at least 1%, by weight, ofthe composition.

Preferred for use herein are salt tolerant thickeners, including but notlimited to: xanthan, guar, hydroxypropyl guar, scleroglucan, methylcellulose, ethyl cellulose (available as AQUACOTE(™)), hydroxyethylcellulose (NATROSOL(™)), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (available as KLUCEL(™)), hydroxyethyl ethylcellulose, cetyl hydroxyethyl cellulose (available as NATROSOL(™) Plus330), N-vinylpyrollidone (available as POVIDONE(™)), Acrylates/Ceteth-20Itaconate Copolymer (available as STRUCTURE(™) 3001), hydroxypropylstarch phosphate (available as STRUCTURE(™) ZEA), polyethoxylatedurethanes or polycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDIcopolymer (available as ACULYN(™) 44), PEG-150/Stearyl/SMDI copolymeravailable as ACULYN(™) 46), trihydroxystearin (available as THIXCIN(™)),acrylates copolymer (e.g. available as ACULYN(™) 33) or hydrophobicallymodified acrylate copolymers (e.g. Acrylates/Steareth-20 MethacrylateCopolymer (available as ACULYN(™) 22), non-ionic amphophilic polymerscomprising at least one fatty chain and at least one hydrophilic unitselected from polyether urethanes comprising at least one fatty chain,and blends of Ceteth—10 phosphate, Di-cetyl phosphate and Cetearylalcohol (available as CRODAFOS(™) CES).

G. Chelants

The inventive compositions may comprise chelants in an amount sufficientto reduce the amount of metals available to interact with formulationcomponents, particularly oxidizing agents, more particularly peroxides.Typically such an amount will range from at least 0.25%, preferably atleast 0.5%, by weight, of the composition. Suitable chelants for useherein include but are not limited to: diamine-N,N′-dipolyacid,monoamine monoamide-N,N′-dipolyacid, andN,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid chelants(preferably EDDS (ethylenediaminedisuccinic acid)), carboxylic acids(preferably aminocarboxylic acids), phosphonic acids (preferablyaminophosphonic acids) and polyphosphoric acids (in particular straightpolyphosphoric acids), their salts and derivatives.

H. pH Modifiers and Buffering Agents

The inventive compositions may further comprise a pH modifier and/orbuffering agent in an amount that is sufficiently effective to adjustthe pH of the composition to fall within a range from 3 to 13,preferably from 8 to 12, more preferably from 9 to 11. Suitable pHmodifiers and/or buffering agents for use herein include, but are notlimited to: ammonia, alkanolamides such as monoethanolamine,diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,tripropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3,-propandiol and guanidium salts, alkalimetal and ammonium hydroxides and carbonates, preferably sodiumhydroxide and ammonium carbonate, and acidulents such as inorganic andinorganic acids, e.g., phosphoric acid, acetic acid, ascorbic acid,citric acid or tartaric acid, hydrochloric acid, and mixtures thereof.

I. Carbonate Ion Source and Radical Scavenger System

The inventive compositions may comprise a system comprising a source ofcarbonate ions, carbamate ions and or hydrocarbonate ions, and a radicalscavenger, in a sufficient amount to reduce damage to the hair duringthe coloring process. Typically, such an amount will range from 0.1% to15%, preferably 0.1% to 10%, more preferably 1% to 7%, by weight of thecomposition, of the carbonate ion, and from 0.1% to 10%, preferably from1% to 7%, by weight of the composition, of radical scavenger.Preferably, the radical scavenger is present at an amount such that theratio of radical scavenger to carbonate ion is from 1:1 to 1:4. Theradical scavenger is preferably selected such that it is not anidentical species as the alkalizing agent.

Suitable sources for the ions include but are not limited to: sodiumcarbonate, sodium hydrogen carbonate, potassium carbonate, potassiumhydrogen carbonate, guanidine carbonate, guanidine hydrogen carbonate,lithium carbonate, calcium carbonate, magnesium carbonate, bariumcarbonate, ammonium carbonate, ammonium hydrogen carbonate and mixturesthereof. Preferred sources of carbonate ions are sodium hydrogencarbonate and potassium hydrogen carbonate. Also preferred are ammoniumcarbonate, and ammonium hydrogen carbonate.

The radical scavenger is a species that can react with a carbonateradical to convert the carbonate radical by a series of fast reactionsto a less reactive species. Preferably, when the radical scavengercomprises an N atom, it has a pKa>7 to prevent the protonation of thenitrogen. Preferred radical scavengers may be selected from the classesof alkanolamines, amino sugars, amino acids and mixtures thereof, andmay include, but are not limited to: monoethanolamine,3-amino-1-propanol, 4-amino-1-butanol,5-amino-1-pentanol,1-amino-2-propanol, 1-amino-2-butanol, 1-amino-2-pentanol,1-amino-3-pentanol, 1-amino-4-pentanol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine,N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine,histidine, serine, tryptophan and potassium, sodium and ammonium saltsof the above and mixtures thereof. Other preferred radical scavengercompounds include benzylamine, glutamic acid, imidazole,di-tert-butylhydroxytoluene, hydroquinone, catechol and mixturesthereof.

III. Methods of Manufacture

The compounds of this invention may be obtained using conventionalmethods. A general description of how to make the compounds is providedabove and specific examples are provided below. The compositions of thisinvention may also be obtained using conventional methods. The keratindyeing compositions may be formed as solutions, preferably as aqueous oraqueous-alcohol solutions. The hair dye product compositions maypreferably be formed as thick liquids, creams, gels, or emulsions whosecomposition is a mixture of the dye compound and other dye ingredientswith conventional cosmetic additive ingredients suitable for theparticular preparation.

IV. Methods of Use

The inventive keratin dyeing compositions may be used by admixing themwith a suitable oxidant, which reacts with the oxidative dye precursorsto develop the hair dye product composition. The oxidant is usuallyprovided in an aqueous composition, which normally is provided as aseparate component of the finished keratin dyeing product system andpresent in a separate container. Upon mixing the keratin dyeingcomposition, the adjuvants are provided in the hair dye composition asit is applied to the hair to achieve desired product attributes, e.g.,pH, viscosity, rheology, etc.

The keratin dyeing composition, as it is applied to the hair, can beweakly acidic, neutral or alkaline according to their composition,typically having a pH from 6 to 11, preferably from 7 to 10, morepreferably from 8 to 10. The pH of the developer composition istypically acidic, and generally the pH is from 2.5 to 6.5, preferablyfrom 3 to 5. The pH of the hair compositions may be adjusted using a pHmodifier as mentioned above.

In order to use the keratin dyeing composition, the above-describedcompositions are mixed immediately prior to use and a sufficient amountof the mixture is applied to the hair, according to the hair abundance,generally from 60 to 200 grams. Upon such preparation the hair dyecomposition is applied to the hair to be dyed and remains in contactwith the hair for an amount of time effective to dye the hair.Typically, the hair dye composition is allowed to act on the hair for 2to 60, preferably 15 to 45, more preferably, 30 minutes, at atemperature ranging from 15° to 50° C. Thereafter, the hair is rinsedwith water, to remove the hair dye composition and dried. If necessary,the hair is washed with a shampoo and rinsed, e.g., with water or aweakly acidic solution, such as a citric acid or tartaric acid solution,and dried. Optionally, a separate conditioning product may also beprovided.

Together, components of the keratin dyeing composition form a system fordyeing hair. This system may be provided as a kit comprising in a singlepackage separate containers of the keratin dyeing composition componentsor other hair treatment product, and instructions for use.

EXAMPLES

The following are non-limiting examples of the compositions of thepresent invention. The examples are given solely for the purpose ofillustration and are not to be construed as limitations of the presentinvention, as many variations thereof are possible without departingfrom the spirit and scope of the invention, which would be recognized byone of ordinary skill in the art. In the examples, all concentrationsare listed as weight percent, unless otherwise specified.

The following compositions can be used for dyeing hair. The dyeingcomposition is mixed with an equal weight of a 20-volume hydrogenperoxide solution (6% by weight). The resulting mixture is applied tothe hair and permitted to remain in contact with the hair for 30minutes. This dyed hair is then shampooed and rinsed with water anddried.

Common base (CB) for dyeing Ingredients Weight (g) Propylene glycol 9.5Ammonium hydroxide 5 Ethoxydiglycol 4 Ethanolamine 4.5 Oleic acid 1Hexylene glycol 6 Cocamidopropyl betaine 3.5 Oleth-10 0.3 Oleth-2 0.3Dilinoleic acid 1.5 C12-C15 Pareth-3 0.5 Soytrimonium chloride 7 Sodiummetasilicate 0.05 Erythorbic acid 0.5 EDTA 0.03 Sodium sulfite 0.31-Phenyl-3-methyl-5-pyrazolone 0.2

Ingredients 1 2 3 4 5 6 7 2-Methylimidazo[1,2- 0.05 0.04 0.03 0.01 0.050.15 0.2 c]pyrimidine-3,5,7- triamine N,N-Bis(2-hydroxyetyl)-p- 0.1 0.02phenylendiamine 4-Aminophenol 0.2 0.02 0.3 0.2 0.44-Amino-2-methylphenol 0.4 0.2 3-Aminophenol 0.1 5-Amino-2-methylphenol0.02 0.02 0.02 0.04 1-Naphthol 0.05 Resorcinol 0.15 0.1 0.1 0.4 0.1 0.50.4 2-Methylresorcinol 0.4 1-Hydroxyethyl-4,5- 0.2 diaminopyrazoleCommon base (CB) 44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qsqs qs qs qs qs

Ingredients 8 9 10 11 12 13 14 pyrrolo[1,2-b]pyridazine- 0.3 0.2 0.2 0.10.1 0.2 0.6 5-amine N,N-Bis(2-hydroxyetyl)-p- 0.33 0.02 phenylendiamine4-Aminophenol 0.5 0.7 0.9 1.2 0.3 4-Amino-2-methylphenol 1 1.23-Aminophenol 0.3 5-Amino-2-methylphenol 0.4 0.4 2.5 2.5 1 0.81-Naphthol Resorcinol 0.3 0.1 0.1 0.1 0.1 0.6 0.1 2-Methylresorcinol 0.40.6 0.6 1-Hydroxyethyl-4,5- 0.2 0.2 0.4 diaminopyrazole Common base (CB)44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qs qs

Ingredients 15 16 17 18 19 20 21 pyrrolo[1,2-c]pyrimidine- 1 0.1 0.5 0.50.1 0.1 0.5 5-amin N,N-Bis(2-hydroxyetyl)-p- 0.1 phenylendiamine4-Aminophenol 0.4 0.8 0.1 4-Amino-2-methylphenol 0.6 0.8 3-Aminophenol1.5 1 0.1 5-Amino-2-methylphenol 1.4 0.5 0.1 0.1 1-Naphthol 0.1 0.1 0.1Resorcinol 0.5 0.2 0.2 0.5 2-Methylresorcinol 0.5 0.8 0.11-Hydroxyethyl-4,5- 0.6 2 1.5 diaminopyrazole Common base (CB) 44.1844.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qs qs

Ingredients 22 23 24 25 26 27 28 7-Hydroxyimidazo[1,5- 0.3 0.5 0.4 0.3c]pyrimidin-5(6H)-one 7-Hydroxy-3- 0.5 0.4 0.3 methylimidazo[1,5-c]pyrimidin-5(6H)-one N,N-Bis(2-hydroxyetyl)-p- 0.1 0.1 0.3 0.1 0.3phenylendiamine p-Phenylenediamine 0.4 0.4 4-Aminophenol 0.5 0.1 0.2 0.10.2 4-Amino-2-methylphenol 1 1 3-Aminophenol 0.3 0.2 0.25-Amino-2-methylphenol 0.4 0.2 0.5 0.4 0.2 0.5 1-Naphthol 0.1 0.1Resorcinol 0.3 0.2 0.4 0.3 0.2 0.4 0.3 2-Methylresorcinol 0.4 0.2 0.21-Hydroxyethyl-4,5- 0.5 0.1 0.3 0.5 0.1 0.3 diaminopyrazole Common base(CB) 44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qsqs

Ingredients 29 30 31 32 33 34 35 Imidazo[1,2-a]pyrimidine- 0.3 0.5 0.40.3 5,7-diol Imidazo[1,2-a]pyrimidin- 0.5 0.4 0.3 5,7-diamineN,N-Bis(2-hydroxyetyl)-p- 0.1 0.1 0.3 0.1 0.3 phenylendiaminep-Phenylenediamine 0.4 0.4 4-Aminophenol 0.5 0.1 0.2 0.1 0.24-Amino-2-methylphenol 1 1 3-Aminophenol 0.3 0.2 0.25-Amino-2-methylphenol 0.4 0.2 0.5 0.4 0.2 0.5 1-Naphthol 0.1 0.1Resorcinol 0.3 0.2 0.4 0.3 0.2 0.4 0.3 2-Methylresorcinol 0.4 0.2 0.21-Hydroxyethyl-4,5- 0.5 0.1 0.3 0.5 0.1 0.3 diaminopyrazole Common base(CB) 44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qsqs

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

All documents cited in the Background, Summary of the Invention, andDetailed Description of the Invention are, in relevant part,incorporated herein by reference; the citation of any document is not tobe construed as an admission that it is prior art with respect to thepresent invention.

1. A keratin dyeing composition comprising: (A) a medium suitable fordyeing; and (B) one or more bicyclic 5-6 heteroaromatic keratin dyeingcompounds with one ring junction nitrogen and one or two extraheteroatoms wherein said bicyclic 5-6 heteroaromatic keratin dyeingcompound with one ring junction nitrogen and one or two extraheteroatoms is an unsubstituted or substituted member selected from thegroup consisting of H-pyrrolo[1,2-b]pyridazine,H-pyrrolo[1,2-f]pyrimidine, H-pyrrolo[1,2-a]pyrazine,H-pyrrolo[1,2-a]pyrimidine, H-imidazo[1,5-a]pyridine,pyrazolo[1,5-b]pyridazine, pyrazolo[1,5-f]pyrimidine,pyrazolo[1,5-a]pyrazine, imidazo[1,5-b]pyridazine,imidazo[1,5-f]pyrimidine, imidazo[1,5-a]pyrazine,imidazo[1,5-a]pyrimidine, imidazo[1,2-b]pyridazine,imidazo[1,2-f]pyrimidine, imidazo[1,2-a]pyrazine, and imidazo[1,2-a]pyrimidine.
 2. The composition of claim 1 wherein said bicyclic5-6 heteroaromatic keratin dyeing compound with one ring junctionnitrogen and one or two extra heteroatoms is selected from the groupconsisting of compounds according to the following formulas:

wherein D² and D⁵ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiodiazolyl; wherein E¹,E², E³, E⁴, E⁵ and E⁶ are each independently selccted from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propioniyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiodiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 3. The composition of claim 1wherein said bicyclic 5-6 heteroaromatic keratin dyeing compound withone ring junction nitrogen and one or two extra heteroatoms is selectedfrom the group consisting of compounds according to the followingformulas:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxyl,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiodiazolyl; wherein E¹, E², E³, E⁴, E⁵ and E⁷ are each independentlyselected from the group consisting of hydrogen, chlorine, bromine,fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionlyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiodiazolyl, phenyl,sulfonyl, sulphonamido, and ureido; wherein at least one of the E⁵ or E⁷in formula IIa and IIc selected from the group consisting of amino,hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxylmethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiodiazolyl.
 4. Thecompositionl of claim 1 wherein said bicyclic 5-6 hetoroaromatic keratindyeing compound with one ring junction nitrogen and one or two extraheteroatoms is selected from the group consisting of compounds accordingto the following formulas:

wherein D² and D⁷ are each independently selected from the groupconsisting of amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino,N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,N-benzylamino, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiodiazolyl; wherein E¹,E², E³, E⁴, E⁶ and E⁷ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofulyl, pyrazolyl, triazolyl,tetrazolyl, traizolyl, oxazolyl, imidazolyl, thiodiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 5. The composition of claim 1wherein said bicyclic 5-6 heteroaromatic keratin dyeing compound withone ring junction nitrogen and one or two extra heteroatoms is selectedfrom the group consisting of compounds according to the followingformulas:

wherein D² is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-benzylamino, methoxy, ethoxy, propyloxy,benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl andthiodiazolyl; wherein E¹, E², E³, E⁴, E⁵ and E⁷ are each independentlyselected from the group consisting of hydrogen, chlorine, bromine,fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, carboxyl, methoxy,ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamidol, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiodiazolyl, phenyl,sulfonyl, sulphonamido, and ureido; wherein at least one of the E⁵ or E⁷in formula IVa and IVc is selected from the group consisting of amino,hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-benzylamino,methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy,phenoxy, methylthio, ethylthio, propylthio, furyl, pyrazolyl, triazolyl,oxazolyl, imidazolyl and thiodiazolyl.
 6. The compositionl of claim 1further comprising at least one five-membered ring developer selectedfrom the group consisting of thiophenes, pyrroles, furans, pyrazoles,imidazoles, thiazoles, oxazoles, isothiaozoles, and isoxazoles.
 7. Thecomposition of claim 6 wherein said five-membered ring developer is apyrazole.
 8. The compositions of claim 7 wherein said five-membered ringdeveloper is selected from the group consisting of1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine, and1-hydroxyethyl-4,5-diaminopyrazole sulphate.
 9. The composition of claim8 wherein said five-membered ring developer is selected from the groupconsisting of 1-methyl1H-pyrazole-4,5-diamine;1-hydroxyethyl-4,5-diaminopyrazole sulphate; and2-(4,5-diamino-1H-pyrazol-1-yl)ethanol.
 10. The composition of claim 1further comprising auxiliary developers.
 11. The composition of claim 1further comprising auxiliary couplers.
 12. The composition of claim 1further comprising direct dyes.
 13. The composition of claim 1 furthercomprising at least one additional component selected from the groupconsisting of oxidizing agents, thickeners, chelants, pH modifiers,buffering agents, and carbonate ion source and radical scavengersystems.
 14. A method of dyeing hair comprising the steps of (a)applylng the composition of claim 1; and (b) rinsing hair.
 15. A kitcomprising (a) the composition of claim 1; (b) an oxidizing agent; and(c) auxiliary couplers and/or auxiliary developers.
 16. A keratin dyeingcomposition comprising: (A) a medium suitable for dyeing; and (B) one ormore bicyclic 5-6 heteroaromatic keratin dyeing compounds with one ringjunction nitrogen and one or two extra heteroatoms according to thefollowing formulas: